Multi-metallic bulk hydroprocessing catalysts

ABSTRACT

Multi-metallic bulk catalysts and methods for synthesizing the same are provided. The multi-metallic bulk catalysts contain nickel, molybdenum tungsten, yttrium, and optionally, copper, titanium and/or niobium. The catalysts are useful for hydroprocessing, particularly hydrodesulfurization and hydrodenitrogenation, of hydrocarbon feedstocks.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority to and benefit of U.S. ProvisionalApplication No. 63/213,324 filed Jun. 22, 2021, the disclosure of whichis incorporated herein by reference.

FIELD

This disclosure relates to multi-metallic bulk catalysts for use inhydroprocessing of hydrocarbon feeds, as well as methods for preparingsuch catalysts.

BACKGROUND

The hydroprocessing of hydrocarbon feedstocks generally encompasses allprocesses in which a hydrocarbon feedstock is reacted with hydrogen inthe presence of a catalyst and under hydroprocessing conditions,typically, at elevated temperature and elevated pressure.Hydroprocessing includes processes such as hydrodesulfurization,hydrodenitrogenation, hydrodeoxygenation, hydrodemetallation,hydrodearomatization, hydrogenation, hydrogenolysis, hydrotreating,hydroisomerization, and hydrocracking.

Hydroprocessing catalysts usually comprise one or more sulfided Group 6metals with one or more Group 8 to 10 non-noble metals as promoters on arefractory support, such as alumina. Hydroprocessing catalysts that areparticularly suitable for hydrodesulfurization, as well ashydrodenitrogenation, generally comprise molybdenum or tungsten sulfidepromoted with a metal such as cobalt, nickel, iron, or a combinationthereof.

In addition to supported catalysts, hydroprocessing using bulk catalysts(also referred to as “unsupported” catalysts) are also known. Althoughbulk hydroprocessing catalyst compositions have relatively highcatalytic activity relative to conventional supported hydroprocessingcatalysts, there exists a continuous need in the art to develop novelbulk catalyst compositions with further improved hydroprocessingactivity.

Most common base metals for hydrotreating applications are Ni, Co, Mo,and W. We recently reported using titania, niobium, and copper to tailorthe activity and selectivity of bulk catalysts for hydrotreatingapplications. Yttrium, as a trivalent transition metal, has not beenwell studied, although it was reported that yttrium can be used as astabilizer for zirconia, titania, and niobia (see, e.g., U.S. Pat. No.10,843,176). A combination of Ni, Mo, W, and Y, and, optionally, a metalselected from one or more of Cu, Nb, and Ti, can potentially provideinteresting activity and selectivity for hydrotreating applications.

SUMMARY

In a first aspect, there is provided a bulk catalyst precursorcomprising: (a) 1 to 60 wt. % of Ni, on a metal oxide basis; (b) 1 to 40wt. % of Mo, on a metal oxide basis; (c) 5 to 80 wt. % of W, on a metaloxide basis; (d) 0.01 to 30 wt. % of Y, on a metal oxide basis; (e) 0 to20 wt. % of Cu, on a metal oxide basis; (f) 0 to 45 wt. % of Ti, on ametal oxide basis; and (g) 0 to 20 wt. % of Nb, on a metal oxide basis.

In a second aspect, there is provided a sulfided bulk catalystcharacterized in that it is the bulk catalyst precursor described hereinthat has been sulfided.

In a third aspect, there is provided a method for preparing the bulkcatalyst precursor described herein, the method comprising: (a)combining in a reaction mixture: (i) a Ni-containing precursor; (ii) aMo-containing precursor; (iii) a W-containing precursor; (iv) aY-containing precursor; optionally, (v) a Cu-containing precursor, aTi-containing precursor and/or a Nb-containing precursor; (vi)optionally, an organic compound-based component; and (vii) a proticliquid; and (b) reacting the mixture under conditions sufficient tocause precipitation of the bulk catalyst precursor; wherein the steps toprepare the bulk catalyst precursor are carried out at a temperature ofno more than 200° C.

In a fourth aspect, there is provided a method for preparing the bulkcatalyst precursor described herein, the method comprising: (a)combining in a reaction mixture: (i) a Ni-containing precursor; (ii) aMo-containing precursor; (iii) a W-containing precursor; (iv) aY-containing precursor; (v) optionally, a Cu-containing precursor, aTi-containing precursor and/or a Nb-containing precursor; (vi)optionally, an organic compound-based component; and (vii) a proticliquid; and (b) reacting the mixture under conditions sufficient tocause precipitation of an intermediate bulk catalyst precursor; and (c)compositing the intermediate bulk catalyst precursor with a Y-containingprecursor to form the bulk catalyst precursor; wherein the steps toprepare the bulk catalyst precursor are carried out at a temperature ofno more than 200° C.

In a fifth aspect, there is provided a process for hydroprocessing ahydrocarbon feedstock, the process comprising contacting the hydrocarbonfeedstock with hydrogen in the presence of a bulk catalyst athydroprocessing conditions to give at least one product, wherein thebulk catalyst is a derived or derivable from a catalyst precursorcomprising: (a) 1 to 60 wt. % of Ni, on a metal oxide basis; (b) 1 to 40wt. % of Mo, on a metal oxide basis; (c) 5 to 80 wt. % of W, on a metaloxide basis; (d) 0.01 to 30 wt. % of Y, on a metal oxide basis; (e) 0 to20 wt. % of Cu, on a metal oxide basis; and (f) 0 to 45 wt. % of Ti, ona metal oxide basis; and (g) 0 to 20 wt. % of Nb, on a metal oxidebasis.

DETAILED DESCRIPTION Definitions

The term “bulk”, when describing a mixed metal catalyst composition, maybe used interchangeably with “unsupported”, meaning that the catalystcomposition is not of the conventional catalyst form which has apreformed, shaped catalyst support which is then loaded with metals viaimpregnation or deposition.

The term “atmospheric pressure” is used herein to describe an earth airpressure wherein no external pressure modifying means is utilized.Generally, unless practiced at extreme earth altitudes, “atmosphericpressure” is about 1 atmosphere (alternatively, about 14.7 psi or about101 kPa).

The terms “wt. %”, “vol. %” or “mol. %” refer to a weight, volume, ormolar percentage of a component, respectively, based on the totalweight, the total volume, or the total moles of material that includesthe component. In a non-limiting example, 10 moles of component in 100moles of the material is 10 mol. % of component.

Bulk Catalysts and Bulk Catalyst Precursors

Multi-metallic bulk catalyst precursor compositions comprising oxides ofNi, Mo, W, Y, and optionally, Cu, Ti and/or Nb, are provided. Prior touse for hydroprocessing, the catalyst precursor can be sulfided whichconverts metals to metal sulfides. After sulfidation, the compositioncorresponds to/is defined as a “catalyst” for the purposes of the claimsbelow.

The bulk catalyst and/or corresponding bulk catalyst precursor comprisesnickel (Ni), molybdenum (Mo), tungsten (W), yttrium (Y), and,optionally, copper (Cu), titanium (Ti) and/or niobium (Nb) metals. Thebulk catalyst and/or corresponding bulk catalyst precursor may containfrom 1 to 60 wt. % of Ni, such as from 5 to 40 wt. % or from 20 to 60wt. %, on a metal oxide basis; from 1 to 40 wt. % of Mo, such as from 1to 25 wt. % or from 3 to 20 wt. %, on a metal oxide basis; from 5 to 80wt. % of W, such as from 10 to 35 wt. % or from 20 to 75 wt. %, on ametal oxide basis; from 0.01 to 30 wt. % of Y, such as from 0.1 to 30wt. % or from 1 to 30 wt. %, on a metal oxide basis; from 0 to 20 wt. %of Cu, such as from 0.1 to 20 wt. % of Cu or from 1 to 20 wt. % on ametal oxide basis; from 0 to 45 wt. % of Ti, such as from 2 to 45 wt. %,from 5 to 40 wt. %, from 10 to 35 wt. % or 20 to 30 wt. %, on a metaloxide basis; and from 0 to 10 wt. % of Nb, such as from 0.01 to 10 wt.%, from 0.1 to 10 wt. %, or from 1 to 10 wt. %, on a metal oxide basis.Thus, the bulk catalysts disclosed herein have the nomenclatureNi—Mo—W—Y, Ni—Mo—W—Y—Cu, Ni—Mo—W—Y—Ti, Ni—Mo—W—Y—Nb, Ni—Mo—W—Y—Cu—Ti,Ni—Mo—W—Y—Cu—Nb, Ni—Mo—W—Y—Ti—Nb, or Ni—Mo—W—Y—Cu—Ti—Nb, wherein eachmetal is present in amounts specified above.

The molar ratios of metals in the bulk catalyst and/or correspondingbulk catalyst precursor can in principle vary between wide ranges. Themolar ratio of Y/(Ni+Mo+W+Cu+Ti+Nb) in the bulk catalyst and/orcorresponding bulk catalyst precursor can be in a range of from 10:1 to1:100 or from 3:1 to 1:3. The molar ratio of Ni/W in the bulk catalystand/or corresponding bulk catalyst precursor can be in a range of from10:1 to 1:10. The molar ratio of W/Mo in the bulk catalyst and/orcorresponding catalyst precursor can be in a range of 100:1 to 1:100.

The bulk catalyst precursor is a hydroxide and may be characterized ashaving the following chemical formula:

A_(v)[Ni_(1-a-b-c)Y_(a)Cu_(b)Nb_(c)(OH)_(x)(L)P_(y)]_(z)[Mo_(m)W_(1-m)O₄][Ti(OH)_(n)O_(2-n/2)]_(w)

wherein: (i) A is an alkali metal cation, a rare earth metal cation, anammonium cation, an organic ammonium cation, phosphonium cation, or acombination thereof; (ii) L is an organic compound-based component; and(iii) 0<a<1; 0≤b<1; 0≤c<1; a+b+c<1; 0<y≤2/p; 0<x<2; 0≤v<2; 0<z; 0<m<1;0<n<4; 0≤w/(z+1)<10.

The bulk catalyst precursor may be comprised of at least 55 wt. % (atleast 60 wt. %, or at least 70 wt. %, or at least 80 wt. % or at least90 wt. %) of oxides of Ni, Mo, W, and Y prior to sulfiding to form abulk catalyst. In any aspect, the bulk catalyst and/or correspondingbulk catalyst precursor may contain 40 wt. % or less of a bindermaterial. Binder materials may be added to improve the physical and/orthermal properties of the catalyst.

The bulk catalyst and/or corresponding bulk catalyst precursor mayfurther include an organic compound-based component, which may be basedon or derived from at least one organic complexing agent used in thepreparation of the bulk catalyst and/or corresponding bulk catalystprecursor. When an organic compound-based component is present, a molarratio of nickel in the composition to organic compound-based compositioncan be in a range of from 3:1 to 20:1.

The bulk catalyst and/or corresponding bulk catalyst precursor can havea BET specific surface area of at least 20 m²/g, or at least 50 m²/g, orat least 75 m²/g, or at least 100 m²/g. In any aspect, theself-supported catalyst and/or corresponding self-supported catalystprecursor can have a BET surface area of 250 m²/g or less, or 200 m²/gor less, or 175 m²/g or less, or 150 m²/g or less, or 125 m²/g or less.Each of the above lower limits for the BET specific surface area isexplicitly contemplated in conjunction with each of the above upperlimits. The term “BET specific surface area” refers to specific surfacearea as determined from nitrogen adsorption data in accordance with themethod of S. Brunauer, P. H. Emmett and E. Teller (J. Am. Chem. Soc.1938, 60, 309-331).

The bulk catalyst and/or corresponding bulk catalyst precursor can havea pore volume of at least 0.02 cm³/g, or at least 0.03 cm³/g, or atleast 0.04 cm³/g, or at least 0.05 cm³/g, or at least 0.06 cm³/g, or atleast 0.08 cm³/g, or at least 0.09 cm³/g, or at least 0.10 cm³/g, or atleast 0.11 cm³/g, or at least 0.12 cm³/g, or at least 0.13 cm³/g, or atleast 0.14 cm³/g, or at least 0.15 cm³/g. In any aspect, theself-supported catalyst and/or corresponding self-supported catalystprecursor can have a pore volume of 0.80 cm³/g or less, or 0.70 cm³/g orless, or 0.60 cm³/g or less, or 0.50 cm³/g or less, or 0.45 cm³/g orless, or 0.40 cm³/g or less, or 0.35 cm³/g or less, or 0.30 cm³/g orless. Each of the above lower limits for the pore volume is explicitlycontemplated in conjunction with each of the above upper limits. Porevolumes are determined from nitrogen adsorption data in accordance withthe procedures described by E. P. Barrett, L. G. Joyner and P. P.Halenda (J. Am. Chem. Soc. 1951, 73, 373-380).

The bulk catalyst and/or corresponding bulk catalyst precursor can havea particle density of at least 1.00 g/cm³ (e.g., at least 1.10 g/cm³, orat least 1.20 g/cm³, or at least 1.30 g/cm³, or at least 1.40 g/cm³, orat least 1.50 g/cm³, or at least 1.60 g/cm³). In any aspect, theself-supported catalyst and/or corresponding self-supported catalystprecursor can have a particle density of 3.00 g/cm³ or less (e.g., 2.90g/cm³ or less, or 2.80 g/cm³ or less, or 2.70 g/cm³ or less, or 2.60g/cm³ or less, or 2.50 g/cm³ or less, or 2.40 g/cm³ or less, or 2.30g/cm³ or less, or 2.20 g/cm³ or less). Each of the above lower limitsfor the particle density is explicitly contemplated in conjunction witheach of the above upper limits. Particle density (D) is obtained byapplying the formula D=M/V, where M is the weight and V is the volume ofthe catalyst sample. The volume is determined by measuring volumedisplacement by submersing the sample into mercury under 28 mm Hgvacuum.

The bulk catalyst and/or corresponding bulk catalyst precursor may becharacterized via powder X-ray diffraction as a poorly crystallinematerial having broad diffraction peaks of low intensity. As usedherein, a broad diffraction peak means a peak having a full width athalf maximum (FWHM) of more than 1° (in 2-theta scale).

Preparation of the Bulk Catalysts and Catalyst Precursors

The present bulk catalyst precursor is a hydroxide and is prepared by amethod wherein the steps prior to sulfiding to form a bulk catalyst arecarried out a temperature of no more than 200° C. and wherein thecatalyst precursor remains a hydroxide prior to sulfiding to form a bulkcatalyst.

In one aspect, the first step in the preparation of the bulk catalystprecursor is a precipitation or co-gelation step, which involvesreacting in a reaction mixture a nickel and niobium precursor compoundsin solution and molybdenum and tungsten precursor compounds in solutionto obtain a precipitate or co-gel. The precipitation or co-gelation isperformed at a temperature and pH at which the metal precursorsprecipitate or form a co-gel.

When titanium is present, titanium can be introduced via either anin-situ or an ex-situ route. In the in-situ route, a Ti-containingprecursor compound can be added to the reaction mixture to precipitatetitanium during co-precipitation or co-gelation of Ni—Mo—W—Y oxides orNi—Mo—W—Y—Cu oxides or Ni—Mo—W—Y—Nb or Ni—Mo—W—Y—Cu—Nb oxides. In theex-situ route, one or more titanium precursor compounds can becomposited with the precipitate or co-gel of Ni—Mo—W—Y oxides orNi—Mo—W—Y—Cu oxides or Ni—Mo—W—Y—Nb or Ni—Mo—W—Y—Cu—Nb oxides.

In any aspect, in-situ addition of titanium can comprise: (a) combiningin a reaction mixture: (i) a Ni-containing precursor; (ii) aMo-containing precursor; (iii) a W-containing precursor; (iv) aY-containing precursor; (v) a Ti-containing precursor; (vi) optionally,a Cu-containing precursor and/or a Nb-containing precursor; (vii)optionally, an organic compound-based component; and (viii) a proticliquid; and (b) reacting the mixture under conditions sufficient tocause precipitation of the bulk catalyst precursor. The reaction mixturemay be obtained by: (1) preparing a first mixture comprising aNi-containing precursor, a Y-containing precursor, an optionalNb-containing precursor and/or an optional Cu-containing precursor, aprotic liquid, and an optional organic compound-based component; (2)preparing a second mixture comprising a Mo-containing precursor, aW-containing precursor, and a protic liquid; (3) adding a Ti-containingprecursor to the first mixture, the second mixture, or a combinationthereof; (4) heating both the first and second mixtures to a temperatureof from 60° C. to 150° C.; (5) combining the first and second mixturestogether. After the reaction step, if necessary, the obtained bulkcatalyst precursor can be separated from the liquid, for example, viafiltration or spray drying.

In any aspect, ex-situ addition of titanium can comprise: (a) combiningin a reaction mixture: (i) a Ni-containing precursor; (ii) aMo-containing precursor; (iii) a W-containing precursor; (iv) aY-containing precursor; (v) optionally, a Cu-containing precursor or aNb-containing precursor; (vi) optionally, an organic compound-basedcomponent; and (vii) a protic liquid; and (b) reacting the mixture underconditions sufficient to cause precipitation of an intermediate bulkcatalyst precursor; and (c) compositing the intermediate bulk catalystprecursor with a Ti-containing precursor to form the bulk catalystprecursor. The reaction mixture may be obtained by: (1) preparing afirst mixture comprising a Ni-containing precursor, a Y-containingprecursor, an optional Cu-containing precursor and/or an optionalNb-containing precursor, a protic liquid, and an optional organiccompound-based component; (2) preparing a second mixture comprising aMo-containing precursor, a W-containing precursor, and a protic liquid;(3) heating both the first and second mixtures to a temperature of from60° C. to 150° C.; and (4) combining the first and second mixturestogether. After the reaction step, if necessary, the obtainedintermediate bulk catalyst can be separated from the liquid, e.g., viafiltration or spray drying.

The temperature at which the catalyst precursor is formed can be in arange of from 60° C. to 150° C. If the temperature is below the boilingpoint of the protic liquid, such as 100° C. in the case of water, theprocess is generally carried out at atmospheric pressure. The reactioncan also be performed under hydrothermal conditions wherein the reactiontemperature is above the boiling temperature of the protic liquid.Typically, such conditions give rise to a pressure above atmosphericpressure and then the reaction is preferably performed in an autoclave,preferably under autogenous pressure, that is without applyingadditional pressure. An autoclave is a device capable of withstandingpressure designed to heat liquids above their boiling temperature. Inany aspect, the bulk catalyst precursor formation process is carried outat one or more temperatures either (a) in a range of from 50° C. to 100°C. under atmospheric pressure or (b) above 100° C. under autogenouspressure.

The reaction time, both under atmospheric and hydrothermal reactionconditions, is chosen sufficiently long to substantially complete thereaction. The reaction times can be very short (e.g., shorter than 1hour with highly reactive reactants). Clearly, longer reaction times,perhaps as long as 24 hours, may be required for raw materials with lowreactivity. The reaction time can in some circumstances vary inverselywith temperature.

Generally, the reaction mixture is kept at its natural pH during thereaction step. The pH can be maintained in a range of from 0 to 12(e.g., from 3 to 9, or from 5 to 8). The pH can be changed to increaseor decrease the rate of precipitation or co-gelation, depending on thedesired characteristics of the product.

The metal precursors can be added to the reaction mixture in solution,suspension or a combination thereof. If soluble salts are added as such,they will dissolve in the reaction mixture and subsequently beprecipitated or co-gelled.

Representative examples of Mo-containing precursor compounds includemolybdenum (di and tri) oxide, molybdic acid, alkali metal molybdates(e.g., sodium molybdate, potassium molybdate), ammonium molybdates(e.g., ammonium molybdate, ammonium dimolybdate, ammoniumheptamolybdate), and heteropolymolybdates (e.g., silicomolybdic acid,phosphomolybdic acid).

Representative examples of W-containing precursor compounds includetungsten (di and tri) oxide, tungstic acid, alkali metal tungstates(e.g., sodium tungstate, potassium tungstate, sodium metatungstate,sodium polytungstate), ammonium tungstates (e.g., ammonium tungstate,ammonium metatungstate, ammonium paratungstate), andheteropolytungstates (e.g., silicotungstic acid, phosphotungstic acid).

Representative examples of Ni-containing precursor compounds includenickel acetate, nickel acetylacetonate, nickel bromide, nickelcarbonate, nickel hydroxycarbonate, nickel bicarbonate, nickel chloride,nickel nitrate, and nickel sulfate.

Representative examples of Y-containing precursor compounds includeyttrium(III) nitrate, yttrium(III) acetate, yttrium(III)acetylacetonate, yttrium(III) hydroxide, yttrium(III) chloride,yttrium(III) bromide, yttrium(III) carbonate, yttrium(III) phosphate,yttrium(III) sulfate, yttrium(iii) isopropoxide, and yttrium(III)butoxide.

Representative examples of Cu-containing precursor compounds includecopper(II) acetate, copper(II) acetylacetonate, copper(II) hydroxide,copper(II) chloride, copper(II) bromide, copper(II) carbonate,copper(II) nitrate, copper(II) phosphate, and copper(II) sulfate.

Representative examples of Nb-containing precursor compounds includeniobium oxalate, ammonium niobium oxalate, niobium chloride, niobiumbromide, niobium ethoxide, niobium n-propoxide, and niobiumisopropoxide.

Any titanium-containing compound suitable for the preparation of a bulkcatalyst of the type described herein may be used as a Ti-containingprecursor compound. The Ti-containing precursor can comprise atetravalent titanium (Ti⁴⁺)-containing compound, a trivalent titanium(Ti³⁺)-containing compound, or a combination thereof.

Representative Ti-containing precursor compounds include TiO₂nanoparticles, colloidal TiO₂, fumed TiO₂, titanium hydroxide,organotitanium compounds, titanium halides, and water-soluble titaniumsalts.

The titanium dioxide nanoparticles may be any type of titanium dioxide.The titanium dioxide can have a high content of anatase and/or rutile.For example, the titanium dioxide may comprise at least 50, or at least55, or at least 60, or at least 65, or at least 70, or at least 75, orat least 80, or at least 85, or at least 90, or at least 95, or at least98, or even at least 99 percent by weight of anatase and/or rutile. Insome embodiments, the titanium dioxide consists essentially of anataseand/or rutile. The titanium dioxide particles preferably have a medianparticle size (D50) of less than 100 nm (e.g., 3 to 50 nm). The titaniumoxide nanoparticles may be introduced in the composition as a solprepared by dispersion in a dispersant, as a water- orsolvent-containing paste, or as a powder. Examples of the dispersantused to prepare a sol include water, alcohols (e.g., methanol, ethanol,isopropanol, n-butanol, isobutanol), and ketones (e.g., methyl ethylketone, methyl isobutyl ketone).

Representative organotitanium compounds include titanium alkoxides ofthe general structure Ti(OR)₄ where each R is independently C1 to C4alkyl and titanium acyl compounds. Representative titanium alkoxidesinclude titanium tetramethoxide, titanium tetraethoxide, titaniumtetra-n-propoxide, titanium tetraisopropoxide, titanium tetra-n-butoxideand titanium tetra-tert-butoxide. Representative titanium acyl compoundsinclude titanium acetylacetonate, titanium oxyacetylacetonate, andtitanium acetate. Other representative organotitanium compounds includethose characterized by the general formula Ti(OR′)₂(acac)₂ wherein eachR′ is independently C1 to C4 alkyl and “acac” is acetylacetonate.

Titanium halides represented by the formula TiX₄ or TiX₃, where X ischloro, bromo, iodo or fluoro, or mixtures thereof, may be used astitanium precursors. In an aspect, the titanium halide is titaniumtetrachloride, titanium tetrabromide, or a combination thereof.

The present disclosure also contemplates the use of organotitaniumhalides such as chlorotitanium triisopropoxide [Ti(O-i-Pr)₃Cl] and thelike as Ti-containing precursor compounds.

Representative water-soluble titanium salts include titanium nitrate andtitanium sulfate.

The organic compound-based component can be an organic compound suitablefor forming metal-ligand complexes in solution. The organiccompound-based component may be selected from an organic acid or saltthereof, a sugar, a sugar alcohol, or a combination thereof.

Representative organic acids include glyoxylic acid, pyruvic acid,lactic acid, malonic acid, oxaloacetic acid, malic acid, fumaric acid,maleic acid, tartaric acid, gluconic acid, citric acid, oxamic acid,serine, aspartic acid, glutamic acid, iminodiacetic acid,ethylenediaminetetraacetic acid, and the like.

Representative sugars include fructose, glucose, galactose, mannose,sucrose, lactose, maltose, and the like, and derivatives thereof.

Representative sugar alcohols include erythritol, xylitol, mannitol,sorbitol, and the like, and derivatives thereof.

The protic liquid can be any protic liquid which does not interfere withthe reactions of the metal compounds. Examples include water, carboxylicacids, and alcohols (e.g., methanol, ethanol, ethylene glycol). Theprotic liquid can be water alone or a mixture of water and an alcohol.

Additional Processing

The bulk catalyst precursor may be subjected to one or more of thefollowing process steps before being used in hydroprocessing processes:(i) compositing with a material selected from the group of bindermaterials, conventional hydroprocessing catalysts, cracking compounds,or mixtures thereof; (ii) spray-drying, (flash) drying, milling,kneading, slurry-mixing, dry or wet mixing, or combinations thereof;(iii) shaping; (iv) drying and/or thermally treating; and (v) sulfiding.The listing of these process steps as (i) to (v) is for convenienceonly; it is not a statement that these processes are constrained to beperformed in this order. These process steps will be explained in moredetail below.

Additional Process Step (i)—Compositing with Further Materials

If so desired, an additional material selected from the group of bindermaterials, conventional hydroprocessing catalysts, cracking compounds,or mixtures thereof can be added during the above-described preparationof the bulk catalyst precursor or the bulk catalyst precursor after itspreparation. Preferably, the material is added subsequent to thepreparation of the bulk catalyst precursor and prior to spray-drying orany alternative technique, or, if spray-drying or the alternativetechniques are not applied, prior to shaping. Optionally, the bulk metalprecursor prepared as described above can be subjected to a solid-liquidseparation before being composited with the material. After solid-liquidseparation, optionally, a washing step can be included. Further, it ispossible to thermally treat the bulk catalyst particles after anoptional solid-liquid separation and drying step and prior to its beingcomposited with the material.

In all the above-described process alternatives, the phrase “compositingthe bulk catalyst precursor with a material” means that the material isadded to the bulk metal particles or vice versa and the resultingcomposition is mixed. Mixing is preferably done in the presence of aliquid (“wet mixing”). This improves the mechanical strength of thefinal bulk catalyst composition.

Compositing the bulk catalyst precursor with the additional materialand/or incorporating the material during the preparation of the catalystprecursor leads to bulk catalyst of particularly high mechanicalstrength, in particular if the median particle size of the bulk metalparticles is in the range of at least 0.5 μm (e.g., at least 1 μm, or atleast about 2 μm) but not more than 5000 μm (e.g., not more than 1000μm, or not more than 500 μm, or not more than 150 μm). The medianparticle diameter of the catalyst precursor can be in a range of 1 to150 μm (e.g., 2 to 150 μm).

The compositing of the bulk metal particles with the material results inbulk metal particles embedded in this material or vice versa. Normally,the morphology of the bulk metal particles is essentially maintained inthe resulting bulk catalyst composition.

The binder materials to be applied may be any materials conventionallyapplied as binders in hydroprocessing catalysts. Examples of bindermaterials include silica, silica-alumina (e.g., conventionalsilica-alumina, silica-coated alumina and alumina-coated silica),alumina (e.g., boehmite, pseudoboehmite, or gibbsite), titania,titania-coated alumina, zirconia, hydrotalcite, or mixtures thereof.Preferred binders are silica, silica-alumina, alumina, titania,titania-coated alumina, zirconia, bentonite, or mixtures thereof. Thesebinders may be applied as such or after peptization.

If alumina is used as binder, the surface area of the alumina can be ina range of 50 to 600 m²/g (e.g., 100 to 450 m²/g), as measured by theBET method. The pore volume of the alumina can be in a range of 0.1 to1.5 cm³/g, as measured by nitrogen adsorption.

Generally, the binder material to be added has less catalytic activitythan the bulk metal particles or no catalytic activity at all. Binderamounts from 0 to 40 wt. % of the total composition can be suitable,depending on the envisaged catalytic application. However, to takeadvantage of the resulting high activity of the bulk metal particles ofthe present disclosure, the binder amounts to be added generally are ina range of 0.1 to 30 wt. % (e.g., 1 to 20 wt. %, or 3 to 20 wt. %, or 4to 12 wt. %) of the total composition.

Additional Process Step (ii)—Spray-Drying, (Flash) Drying, Milling,Kneading, Slurry Mixing, Dry or Wet Mixing

The bulk catalyst precursor optionally comprising any of the above(further) materials can be subjected to spray-drying, (flash) drying,milling, kneading, slurry-mixing, dry or wet mixing, or combinationsthereof, with a combination of wet mixing and kneading or slurry mixingand spray-drying being preferred.

These techniques can be applied either before or after any of the above(further) materials are added (if at all), after solid-liquidseparation, before or after a thermal treatment, and subsequent tore-wetting.

Preferably, the catalyst precursor is both composited with any of theabove materials and subjected to any of the above techniques. It isbelieved that by applying any of the above-described techniques ofspray-drying, (flash) drying, milling, kneading, slurry-mixing, dry orwet mixing, or combinations thereof, the degree of mixing between thecatalyst precursor particles and any of the above materials is improved.This applies to cases where the material is added before as well asafter the application of any of the above-described methods. However, itis generally preferred to add the material prior to step (ii). If thematerial is added subsequent to step (ii), the resulting composition canbe thoroughly mixed by any conventional technique prior to any furtherprocess steps such as shaping. An advantage of spray-drying is that nowaste-water streams are obtained when this technique is applied.

Spray-drying can be carried out at an outlet temperature in the range of100° C. to 200° C. (e.g., 120° C. to 180° C.).

Dry mixing means mixing the catalyst precursor particles in the drystate with any of the above materials in the dry state. Wet mixinggenerally comprises mixing the wet filter cake comprising the catalystprecursor particles and optionally any of the above materials as powdersor wet filter cake to form a homogenous paste thereof.

Additional Process Step (iii)—Shaping

If so desired, the bulk catalyst precursor optionally comprising any ofthe above (further) materials may be shaped optionally after step (ii)having been applied. Shaping comprises extrusion, pelletizing, beadingand/or spray-drying. It is noted that if the bulk catalyst compositionis to be applied in slurry-type reactors, fluidized beds, moving beds,or expanded beds, generally spray-drying or beading is applied. Forfixed-bed or ebullating bed applications, generally the bulk catalystcomposition is extruded, pelletized and/or beaded. In the latter case,at any stage prior to or during the shaping step, any additives whichare conventionally used to facilitate shaping can be added. Theseadditives may comprise aluminum stearate, surfactants, graphite, starch,methyl cellulose, bentonite, polyethylene glycols, polyethylene oxides,or mixtures thereof. Further, when alumina is used as binder, it may bedesirable to add acids such as nitric acid prior to the shaping step topeptize the alumina and to increase the mechanical strength of theextrudates.

If the shaping comprises extrusion, beading and/or spray-drying, it ispreferred that the shaping step is carried out in the presence of aliquid, such as water. For extrusion and/or beading, the amount ofliquid in the shaping mixture, expressed as loss-on-ignition, can be ina range of 20% to 80%.

Additional Process Step (iv)—Drying and/or Thermally Treating

After an optional drying step, preferably above 100° C., the resultingshaped bulk catalyst composition may be thermally treated, if desired. Athermal treatment, however, is not essential to the process of thisdisclosure. A “thermal treatment” according to the present disclosurerefers to a treatment performed at a temperature of from 100° C. to 200°C. for a time varying from 0.5 to 48 hours in an inert gas such asnitrogen, or in an oxygen-containing gas, such as air or pure oxygen.The thermal treatment can be carried out in the presence of water steam.

In all the above process steps the amount of liquid must be controlled.Where, prior to subjecting the bulk catalyst composition tospray-drying, the amount of liquid is too low, additional liquid must beadded. Conversely where, prior to extrusion of the bulk catalystcomposition, the amount of liquid is too high, the amount of liquid mustbe reduced using solid-liquid separation techniques such as filtration,decantation, or evaporation and, if necessary, the resulting materialcan be dried and subsequently re-wetted to a certain extent. For all theabove process steps, it is within the scope of the skilled person tocontrol the amount of liquid appropriately.

Additional Process Step (v)—Sulfiding

The tetrametallic bulk catalyst is generally used in its sulfided form.Catalyst sulfiding can be carried out in any way effective for makingthe catalyst in sulfide form, including conventional sulfiding methods.Sulfidation can be carried out by contacting the catalyst precursor,directly after its preparation or after any one of additional processsteps (i)-(iv), with a sulfur-containing compound such as elementalsulfur, hydrogen sulfide, dimethyl disulfide, or organic or inorganicpolysulfides. The sulfidation step can be carried out in the liquid andthe gaseous phase.

The sulfidation can generally be carried out in-situ and/or ex-situ.Preferably, the sulfidation is carried out in-situ (i.e., thesulfidation is carried out in the hydroprocessing reactor subsequent tothe bulk catalyst precursor composition being loaded into thehydroprocessing unit).

Use in Hydroprocessing

The bulk catalyst precursor of the present disclosure is particularlyuseful for hydroprocessing hydrocarbon feedstocks. Hydroprocessingincludes processes such as hydrodesulfurization, hydrodenitrogenation,hydrodemetallation, hydrodearomatization, hydrogenation, hydrogenolysis,hydrotreating, hydroisomerizaiton, and hydrocracking.

A wide range of petroleum and chemical hydrocarbon feedstocks can behydroprocessed in accordance with the present disclosure. Hydrocarbonfeedstocks include those obtained or derived from crude petroleum oil,from tar sands, from coal liquefaction, from shale oil and fromhydrocarbon synthesis, such as reduced crudes, hydrocrackates,raffinates, hydrotreated oils, atmospheric and vacuum gas oils, cokergas oils, atmospheric and vacuum residua, deasphalted oils, dewaxedoils, slack waxes, Fischer-Tropsch waxes, biorenewable feedstocks, andmixtures thereof. Suitable feedstocks range from relatively lightdistillate fractions up to heavy feedstocks, such as gas oils, lube oilsand residua. Examples of light distillate feedstocks include naphtha(typical boiling range of from about 25° C. to about 210° C.), diesel(typical boiling range of from about 150° C. to about 400° C.), keroseneor jet fuel (typical boiling range of from about 150° C. to about 250°C.) and the like. Examples of heavy feedstocks include vacuum (or heavy)gas oils (typical boiling range of from about 315° C. to about 610° C.),raffinates, lube oils, cycle oils, waxy oils and the like. Preferredhydrocarbon feedstocks have a boiling range of from about 150° C. toabout 650° C. (e.g., from about 150° C. to about 450° C.).

Hydroprocessing conditions can include a temperature of from 200° C. to450° C., or from 315° C. to 425° C.; a pressure of from 250 to 5000 psig(1.7 to 34.6 MPa), or from 300 to 3000 psig (2.1 to 20.7 MPa); a liquidhourly space velocity (LHSV) of from 0.1 to 10 h⁻¹, or from 0.5 to 5h⁻¹; and a hydrogen gas rate of from 100 to 15,000 SCF/B (17.8 to 2672m³/m³), or from 500 to 10,000 SCF/B (89 to 1781 m³/m³).

Hydroprocessing according to the present disclosure can be practiced inone or more reaction zones using any suitable reactor system such as oneor more fixed-bed, moving-bed or fluidized bed reactors. A fixed bedreactor can include one or more vessels, single or multiple beds ofcatalyst in each vessel, and various combinations of hydroprocessingcatalyst in one or more vessels.

EXAMPLES

The following illustrative examples are intended to be non-limiting.

Example 1 (Comparative) Synthesis of Bulk Catalyst Precursor Ni (2.5)-Mo(1)-W(1)

Preparation of Solution A: 45 g of ammonium heptamolybdate and 72 g ofammonium metatungstate were added into 2000 g of deionized water in a 4L flask. The pH was adjusted to 9.8 with ammonia water. The solution wasthen heated to 80° C.

Preparation of Solution B: In a separate 500 mL beaker, 184.5 g ofnickel nitrate and 10.1 of maleic acid were dissolved into 100 g ofdeionized water. Solution B was added into Solution A over 15 minutes.The pH was monitored during addition. Green precipitates formed as soonas Solution B was added. The final pH was at 6.0-7.0 after addition. Theslurry was aged at 80° C. for 4 hours. After ageing, the product wasrecovered by filtration, washed with deionized water, and dried at 130°C. in an oven.

Example 2 (Comparative) Synthesis of Bulk Catalyst Precursor Ni (7.5)-Mo(1)-W(3)

Preparation of Solution A: 10.4 g of ammonium heptamolybdate and 44.8 gof ammonium metatungstate were added into 2000 g of deionized water in a4 L flask. The pH was adjusted to 9.8 with ammonia water. The solutionwas then heated to 80° C.

Preparation of Solution B: In a separate 500 mL beaker, 128.3 g ofnickel nitrate and 5.8 g of maleic acid were dissolved into 100 g ofdeionized water.

Solution B was added into Solution A over 15 minutes. The pH wasmonitored during addition. Green precipitates formed as soon as SolutionB was added. The final pH was at 6.0-7.0 after addition. The slurry wasaged at 80° C. for 4 hours. After ageing, the product was recovered byfiltration, washed with deionized water, and dried at 130° C. in anoven.

Example 3 (Comparative) Synthesis of Bulk Catalyst Precursor Ni (3.8)-Mo(1)-W(1.1)

Preparation of Solution A: 17.6 g of ammonium heptamolybdate and 27.8 gof ammonium metatungstate were added into 2000 g of deionized water in a4 L flask. The pH was adjusted to 9.8 with ammonia water. The solutionwas then heated to 80° C.

Preparation of Solution B: In a separate 500 mL beaker, 110.3 g ofnickel nitrate and 5.8 g of maleic acid were dissolved into 100 g ofdeionized water.

Solution B was added into Solution A over 15 minutes. The pH wasmonitored during addition. Green precipitates formed as soon as SolutionB was added. The final pH was at 6.0-7.0 after addition. The slurry wasaged at 80° C. for 4 hours. After ageing, the product was recovered byfiltration, washed with deionized water, and dried at 130° C. in anoven.

Example 4 (Comparative) Synthesis of Bulk Catalyst PrecursorNi(7)-Mo(1)-W(3)-Nb(0.5)

Preparation of Solution A: 18 g of ammonium heptamolybdate and 79 g ofammonium metatungstate were added into 1875 g of deionized water in a 4L flask. The pH was adjusted to 9.8 with ammonia water. The solution wasthen heated to 80° C.

Preparation of Solution B: In a separate 500 mL beaker, 188 g of nickelnitrate, 16 g of ammonium niobate oxalate, and 10 g of maleic acid weredissolved into 100 g of deionized water.

Solution B was added into Solution A over 15 minutes. The pH wasmonitored during addition. Green precipitates formed as soon as SolutionB was added. The final pH was at 6.0-7.0 after addition. The slurry wasaged at 80° C. for 4 hours. After ageing, the product was recovered byfiltration, washed with deionized water, and dried at 130° C. in anoven.

Example 5 (Comparative) Synthesis of Bulk Catalyst Precursor Ni (6.2)-Mo(1)-W (3)-Nb (1)-Cu (0.3)

Preparation of Solution A: 18 g of ammonium heptamolybdate and 79 g ofammonium metatungstate were added into 1875 g of deionized water in a 4L flask. The pH was adjusted to 9.8 with ammonia water. The solution wasthen heated to 80° C.

Preparation of Solution B: In a separate 500 mL beaker, 166 g of nickelnitrate, 32 g of ammonium niobate oxalate, 8 g of copper(II) nitrate,and 9 g of maleic acid were dissolved into 100 g of deionized water.

Solution B was added into Solution A over 15 minutes. The pH wasmonitored during addition. Green precipitates formed as soon as SolutionB was added. The final pH was at 6.0-7.0 after addition. The slurry wasaged at 80° C. for 4 hours. After ageing, the product was recovered byfiltration, washed with deionized water, and dried at 130° C. in anoven.

Example 6 Synthesis of Bulk Catalyst Precursor Ni(6.2)-Mo(1)-W(3)-Y(1)

Preparation of Solution A: 18 g of ammonium heptamolybdate and 79 g ofammonium metatungstate were added into 1875 g of deionized water in a 4L flask. The pH was adjusted to 9.8 with ammonia water. The solution wasthen heated to 80° C.

Preparation of Solution B: In a separate 500 mL beaker, 174 g of nickelnitrate, 40 g of yttrium(III) nitrate hexahydrate, and 9 g of maleicacid were dissolved into 100 g of deionized water.

Solution B was added into Solution A over 15 minutes. The pH wasmonitored during addition. Green precipitates formed as soon as SolutionB was added. The final pH was at 6.0-7.0 after addition. The slurry wasaged at 80° C. for 4 hours. After ageing, the product was recovered byfiltration, washed with deionized water, and dried at 130° C. in anoven.

Example 7 Synthesis of Bulk Catalyst PrecursorNi(6.5)-Mo(1)-W(3)-Nb(0.5)-Y(0.1)

Preparation of Solution A: 18 g of ammonium heptamolybdate and 79 g ofammonium metatungstate were added into 1875 g of deionized water in a 4L flask. The pH was adjusted to 9.8 with ammonia water. The solution wasthen heated to 80° C.

Preparation of Solution B: In a separate 500 mL beaker, 174 g of nickelnitrate, 4 g of yttrium(III) nitrate hexahydrate, 16 g of ammoniumniobate (V) hydrate, and 10 g of maleic acid were dissolved into 100 gof deionized water.

Solution B was added into Solution A over 15 minutes. The pH wasmonitored during addition. Green precipitates formed as soon as SolutionB was added. The final pH was at 6.0-7.0 after addition. The slurry wasaged at 80° C. for 4 hours. After ageing, the product was recovered byfiltration, washed with deionized water, and dried at 130° C. in anoven.

Example 8 Synthesis of Bulk Catalyst Precursor Ni(6.5)-Mo(1)-W(3)-Y(0.1)

Preparation of Solution A: 18 g of ammonium heptamolybdate and 79 g ofammonium metatungstate were added into 1875 g of deionized water in a 4L flask. The pH was adjusted to 9.8 with ammonia water. The solution wasthen heated to 80° C.

Preparation of Solution B: In a separate 500 mL beaker, 174 g of nickelnitrate, 4 g of yttrium(III) nitrate hexahydrate, and 10 g of maleicacid were dissolved into 100 g of deionized water.

Solution B was added into Solution A over 15 minutes. The pH wasmonitored during addition. Green precipitates formed as soon as SolutionB was added. The final pH was at 6.0-7.0 after addition. The slurry wasaged at 80° C. for 4 hours. After ageing, the product was recovered byfiltration, washed with deionized water, and dried at 130° C. in anoven.

Example 9 Synthesis of Bulk Catalyst PrecursorNi(6.5)-Mo(1)-W(3)-Nb(0.5)-Y(0.5)

Preparation of Solution A: 18 g of ammonium heptamolybdate and 79 g ofammonium metatungstate were added into 1875 g of deionized water in a 4L flask. The pH was adjusted to 9.8 with ammonia water. The solution wasthen heated to 80° C.

Preparation of Solution B: In a separate 500 mL beaker, 174 g of nickelnitrate, 20 g of yttrium(III) nitrate hexahydrate, 16 g of ammoniumniobate (V) hydrate, and 10 g of maleic acid were dissolved into 100 gof deionized water.

Solution B was added into Solution A over 15 minutes. The pH wasmonitored during addition. Green precipitates formed as soon as SolutionB was added. The final pH was at 6.0-7.0 after addition. The slurry wasaged at 80° C. for 4 hours. After ageing, the product was recovered byfiltration, washed with deionized water, and dried at 130° C. in anoven.

Example 10 Synthesis of Bulk Catalyst PrecursorNi(4.5)-Mo(1)-W(3)-Y(1)-Nb(1)-Cu(0.3)-Ti(5.5)

Preparation of Solution A: 35 g of ammonium heptamolybdate and 151 g ofammonium metatungstate were added into 2500 g of deionized water in a 4L flask. The pH was adjusted to 9.8 with ammonia water. The solution wasthen heated to 80° C.

Preparation of Solution B: In a separate 1 L beaker, 389 g of nickelnitrate, 113 g of yttrium nitrate hexahydrate, 60 g of ammonium niobateoxalate, 14 g of copper nitrate trihydrate and 20 g of maleic acid weredissolved into 800 g of deionized water.

Solution B was added into Solution A over 30 minutes. The pH wasmonitored during addition. Green precipitates formed as soon as SolutionB was added. The final pH was at 6.0-7.0 after addition. The slurry wasaged at 80° C. for 4 hours. After ageing, the product was recovered byfiltration. The filter cake and 87 g of TiO₂ (Venator Hombikat 8602)were mixed into homogeneous phase and stirred at 80° C. for 2 hours. Themixture was recovered by filtration, washed with deionized water anddried at 130° C. in an oven.

Example 11 Synthesis of Bulk Catalyst PrecursorNi(4.5)-Mo(1)-W(3)-Y(1)-Cu(1)-Ti(5.5)

Preparation of Solution A: 35 g of ammonium heptamolybdate and 151 g ofammonium metatungstate were added into 2500 g of deionized water in a 4L flask. The pH was adjusted to 9.8 with ammonia water. The solution wasthen heated to 80° C.

Preparation of Solution B: In a separate 1 L beaker, 389 g of nickelnitrate, 113 g of yttrium nitrate hexahydrate, 46 g of copper nitratetrihydrate and 20 g of maleic acid were dissolved into 800 g ofdeionized water.

Solution B was added into Solution A over 30 minutes. The pH wasmonitored during addition. Green precipitates formed as soon as SolutionB was added. The final pH was at 6.0-7.0 after addition. The slurry wasaged at 80° C. for 4 hours. After ageing, the product was recovered byfiltration. The filter cake and 87 g of TiO₂ (Venator Hombikat 8602)were mixed into homogeneous phase and stirred at 80° C. for 2 hours. Themixture was recovered by filtration, washed with deionized water anddried at 130° C. in an oven.

Example 12 Production of Extrudates

Prior to catalytic evaluation, catalyst precursors were shaped intoextrudates. Dried catalyst precursor was ground to a fine powder (<100mesh) and mixed with a proper amount of a binder and water to make anextrudable mixture, followed by extrusion on a Carver press.

Example 13 Bulk Catalyst Precursor Characterization

The particle density (D), BET surface area (SA) and pore volume (PV)were measured for the bulk catalyst precursors of Examples 1-11. Theresults are shown in Table 1 below and indicate that addition of niobiumcan decrease particle density.

TABLE 1 Catalyst Precursor Properties PD N₂ BET SA N₂ PV PrecursorComposition [g/cm³] [m²/g] [cm³/g] Ex. 1 Ni(2.5)—Mo(1)—W(1) 2.77 1260.09 Ex. 2 Ni(7.5)—Mo(1)—W(3) 2.45 134 0.10 Ex. 3 Ni(3.8)—Mo(1)—W(1.1)1.93 160 0.11 Ex. 4 Ni(7)—Mo(1)—W(3)—Nb(0.5) 2.28 103 0.10 Ex. 5Ni(6.2)—Mo(1)—W(3)—Nb(1)—Cu(0.3) 2.26 100 0.10 Ex. 6Ni(6.2)—Mo(1)—W(3)—Y(1) 1.39 149 0.31 Ex. 7Ni(6.5)—Mo(1)—W(3)—Nb(0.5)—Y(0.1) 1.86 135 0.25 Ex. 8Ni(6.5)—Mo(1)—W(3)—Y(0.1) 1.90 140 0.26 Ex. 9Ni(6.5)—Mo(1)—W(3)—Nb(0.5)—Y(0.5) 1.64 152 0.33 Ex. 10Ni(4.5)—Mo(1)—W(3)—Y(1)—Nb(1)—Cu(0.3)—Ti(5.5) 1.36 169 0.35 Ex. 11Ni(4.5)—Mo(1)—W(3)—Y(1)—Cu(1)—Ti(5.5) 1.34 170 0.36

1. A bulk catalyst precursor comprising: (a) 1 to 60 wt. % of Ni, on ametal oxide basis; (b) 1 to 40 wt. % of Mo, on a metal oxide basis; (c)5 to 80 wt. % of W, on a metal oxide basis; (d) 0.01 to 30 wt. % of Y,on a metal oxide basis; (e) 0 to 20 wt. % of Cu, on a metal oxide basis;(f) 0 to 45 wt. % of Ti, on a metal oxide basis; and (g) 0 to 20 wt. %of Nb, on a metal oxide basis.
 2. The bulk catalyst precursor of claim1, further comprising an organic compound-based component.
 3. The bulkcatalyst precursor of claim 2, wherein the organic compound-basedcomponent is selected from the group of an organic acid or salt thereof,a sugar, a sugar alcohol, or a combination thereof.
 4. The bulk catalystprecursor of claim 2, wherein the organic compound-based component isselected from the group of glyoxylic acid, pyruvic acid, lactic acid,malonic acid, oxaloacetic acid, malic acid, fumaric acid, maleic acid,tartaric acid, gluconic acid, citric acid, oxamic acid, serine, asparticacid, glutamic acid, iminodiacetic acid, ethylenediaminetetraaceticacid, fructose, glucose, galactose, mannose, sucrose, lactose, maltose,erythritol, xylitol, mannitol, sorbitol, or a combination thereof. 5.The bulk catalyst precursor of claim 2, wherein a molar ratio of Ni tothe organic compound-based component is in a range of 3:1 to 20:1. 6.The bulk catalyst precursor of claim 1, wherein a molar ratio ofY/(Ni+Mo+W+Cu+Ti+Nb) is in a range of from 10:1 to 1:100.
 7. The bulkcatalyst precursor of claim 1, wherein a molar ratio of Ni/W is in arange of 10:1 to 1:10.
 8. The bulk catalyst precursor of claim 1,wherein a molar ratio of W/Mo is in a range of 100:1 to 1:100.
 9. Thebulk catalyst precursor of claim 1, wherein the bulk catalyst precursoris of formula:A_(v)[Ni_(1-a-b-c)Y_(a)Cu_(b)Nb_(c)(OH)_(x)(L)P_(y)]_(z)[Mo_(m)W_(1-m)O₄][Ti(OH)_(n)O_(2-n/2)]_(w)wherein: (i) A is an alkali metal cation, a rare earth metal cation, anammonium cation, an organic ammonium cation, phosphonium cation, or acombination thereof; (ii) L is an organic compound-based component; and(iii) 0<a<1; 0≤b<1; 0≤c<1; a+b+c<1; 0<y≤2/p; 0<x<2; 0≤v<2; 0<z; 0<m<1;0<n<4; 0≤w/(z+1)<10.
 10. The bulk catalyst precursor of claim 1, furthercomprising 1 to 15 wt. % of a binder.
 11. The bulk catalyst precursor ofclaim 1, having one or more of the following properties: a BET specificsurface area of from 50 to 250 m²/g; a pore volume of from 0.02 to 0.80cm³/g; and particle density of 1.00 to 3.00 cm³/g.
 12. A sulfided bulkcatalyst characterized in that it is a bulk catalyst precursor accordingto claim 1 that has been sulfided.
 13. A method for preparing the bulkcatalyst precursor of claim 1, the method comprising: (a) combining in areaction mixture: (i) a Ni-containing precursor; (ii) a Mo-containingprecursor; (iii) a W-containing precursor; (iv) a Y-containingprecursor; (v) optionally, a Cu-containing precursor, a Ti-containingprecursor and/or a Nb-containing precursor; (vi) optionally, an organiccompound-based component; and (vii) a protic liquid; and (b) reactingthe mixture under conditions sufficient to cause precipitation of thebulk catalyst precursor; wherein the steps to prepare the bulk catalystprecursor are carried out at a temperature of no more than 200° C. 14.The method of claim 13, wherein the reaction mixture is prepared by:preparing a first mixture comprising a Ni-containing precursor, aY-containing precursor, an optional Cu-containing precursor, an optionalNb-containing precursor, a protic liquid, and an optional organiccompound-based component; preparing a second mixture comprising aMo-containing precursor, a W-containing precursor, and a protic liquid;optionally, adding a Ti-containing precursor to the first mixture, thesecond mixture, or a combination thereof; heating both the first andsecond mixtures to a temperature of from 60° C. to 150° C.; combiningthe first and second mixtures together.
 15. The method of claim 14,wherein the Ti-containing precursor is selected from TiO₂ nanoparticles,colloidal TiO₂, fumed TiO₂, titanium hydroxide, organotitaniumcompounds, titanium halides, organotitanium halides, water-solubletitanium salts, or a combination thereof.
 16. A method for preparing thebulk catalyst precursor of claim 1, the method comprising: (a) combiningin a reaction mixture: (i) a Ni-containing precursor; (ii) aMo-containing precursor; (iii) a W-containing precursor; (iv) aY-containing precursor; (v) optionally, a Cu-containing precursor and/ora Nb-containing precursor; (vi) optionally, an organic compound-basedcomponent; and (vii) a protic liquid; and (b) reacting the mixture underconditions sufficient to cause precipitation of an intermediate bulkcatalyst precursor; and (c) compositing the intermediate bulk catalystprecursor with a Ti-containing precursor to form the bulk catalystprecursor; wherein the steps to prepare the bulk catalyst precursor arecarried out at a temperature of no more than 200° C.
 17. The method ofclaim 16, wherein the reaction mixture is prepared by: preparing a firstmixture comprising a Ni-containing precursor, a Y-containing precursor,an optional Cu-containing precursor, an optional Nb-containingprecursor, a protic liquid, and an optional organic compound-basedcomponent; preparing a second mixture comprising a Mo-containingprecursor, a W-containing precursor, and a protic liquid; heating boththe first and second mixtures to a temperature of from 60° C. to 150°C.; and combining the first and second mixtures together.
 18. The methodof claim 16, wherein the Ti-containing precursor is selected from TiO₂nanoparticles, fumed TiO₂, or a combination thereof.
 19. The method ofclaim 16, wherein the intermediate bulk catalyst precursor is aNi—Mo—W—Y, Ni—Mo—W—Y—Cu, Ni—Mo—W—Y—Nb, or Ni—Mo—W—Y—Cu—Nb bulk catalystprecursor.
 20. The method of claim 13 or claim 16, wherein the reactingis carried out at one or more temperatures either (a) in a range of 60°C. to 100° C. under atmospheric pressure or (b) above 100° C. underautogenous pressure.
 21. The method of claim 13 or claim 16, wherein theorganic compound-based component is selected from an organic acid orsalt thereof, a sugar, a sugar alcohol, or a combination thereof. 22.The method of claim 21, wherein the organic compound-based component isselected from glyoxylic acid, pyruvic acid, lactic acid, malonic acid,oxaloacetic acid, malic acid, fumaric acid, maleic acid, tartaric acid,gluconic acid, citric acid, oxamic acid, serine, aspartic acid, glutamicacid, iminodiacetic acid, ethylenediaminetetraacetic acid, fructose,glucose, galactose, mannose, sucrose, lactose, maltose, erythritol,xylitol, mannitol, sorbitol, or a combination thereof.
 23. The method ofclaim 13 or claim 16, further comprising one or more of the followingsteps: compositing the bulk catalyst precursor with 0 to 40 wt. % with amaterial selected from the group of binder materials, conventionalhydroprocessing catalysts, cracking compounds, or mixtures thereof;spray-drying, (flash) drying, milling, kneading, slurry-mixing, dry orwet mixing, or combinations thereof; shaping, drying and/or thermallytreating at a temperature of no more than 200° C.; or sulfiding.
 24. Aprocess for hydroprocessing a hydrocarbon feedstock, the processcomprising contacting the hydrocarbon feedstock with hydrogen in thepresence of a bulk catalyst at hydroprocessing conditions to give atleast one product, wherein the bulk catalyst is a derived or derivablefrom a bulk catalyst precursor comprising: (a) 1 to 60 wt. % of Ni, on ametal oxide basis; (b) 1 to 40 wt. % of Mo, on a metal oxide basis; (c)5 to 80 wt. % of W, on a metal oxide basis; (d) 0.01 to 30 wt. % of Y,on a metal oxide basis; (e) 0 to 20 wt. % of Cu, on a metal oxide basis;(f) 0 to 45 wt. % of Ti, on a metal oxide basis; and (g) 0 to 20 wt. %of Nb, on a metal oxide basis.
 25. The process of claim 24, wherein thehydroprocessing is selected from the group consisting ofhydrodesulfurization, hydrodenitrogenation, hydrodeoxygenation,hydrodemetallation, hydrodearomatization, hydrogenation, hydrogenolysis,hydrotreating, hydroisomerization, and hydrocracking.
 26. The process ofclaim 24, wherein the hydroprocessing conditions include a temperatureof from 200° C. to 450° C.; a pressure of from 250 to 5000 psig (1.7 to34.6 MPa); a liquid hourly space velocity of from 0.1 to 10 h⁻¹; and ahydrogen gas rate of from 100 to 15,000 SCF/B (17.8 to 2672 m³/m³).